CN114604860A - Graphene film growth substrate and preparation method and application thereof - Google Patents
Graphene film growth substrate and preparation method and application thereof Download PDFInfo
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- CN114604860A CN114604860A CN202210252457.6A CN202210252457A CN114604860A CN 114604860 A CN114604860 A CN 114604860A CN 202210252457 A CN202210252457 A CN 202210252457A CN 114604860 A CN114604860 A CN 114604860A
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- C01B32/182—Graphene
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- C01B32/186—Preparation by chemical vapour deposition [CVD]
Abstract
The invention relates to a graphene film growth substrate and a preparation method and application thereof. The preparation method of the graphene film growth substrate comprises the following steps: providing a copper foil substrate, wherein the copper foil substrate is provided with a first surface and a second surface opposite to the first surface; carrying out protective film pasting treatment on the first surface, and carrying out oxidation treatment on the second surface to prepare an intermediate I; and removing the protective film to expose the first surface. The method is simple to operate, can reduce the content of carbon impurities in the substrate, remarkably improves the single-layer rate of graphene, can be carried out in a large batch in a roll-to-roll mode, remarkably improves the production efficiency of the copper foil substrate of the substrate, can be used for preparing the copper foil substrate in a large batch, and is combined with a preparation method of a large-batch graphene film to improve the production efficiency of the graphene film.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a graphene film growth substrate and a preparation method and application thereof.
Background
Due to good physicochemical properties of graphene, such as ultrahigh carrier mobility, high light transmittance, good mechanical properties and the like, the graphene is widely researched and shows potential practical values in the fields of transparent conductive films, photoelectric detection, catalysis, biological detection and the like. Heretofore, production methods such as a mechanical lift-off method, a silicon carbide epitaxial method, a liquid phase lift-off method, a redox method, a Chemical Vapor Deposition (CVD) method, and a bottom-up synthesis method have been developed. The methods have advantages and are suitable for different occasions, wherein the chemical vapor deposition method for the surface of the copper foil has the advantages of high quality of the grown graphene, suitability for macro preparation and the like.
The quality of the graphene film prepared by the chemical vapor deposition method is greatly influenced by the copper foil substrate, while the common commercial copper foil is generally polycrystalline, has impurities and has high roughness. This can cause a large amount of grain boundaries, defects and wrinkles in the graphene thin film, which greatly limits the application of graphene. The common treatment such as cleaning or electrochemical polishing of the copper foil can reduce the surface impurities of the copper foil to a certain extent and reduce the surface roughness, thereby improving the preparation quality of the graphene. However, in the actual production process, the electrochemical polishing step is complicated and takes a long time.
In addition, in the existing copper foil preparation process, the copper foil substrate is difficult to carry out in a roll-to-roll mode, particularly in the electrochemical polishing process, and the polishing can be usually carried out only once. The method brings great difficulty to the subsequent large-batch roll-to-roll production and preparation of the graphene, and cannot meet the great demand of the graphene film at present.
Therefore, the method for preparing the single-layer graphene growth substrate which is simple, effective and capable of being processed in large batch is explored, and the method has important significance for improving the quality of the graphene film and enabling the preparation of the graphene film to be large-scale.
Disclosure of Invention
Based on the method, the invention provides the preparation method of the graphene film growth substrate, which can reduce the content of carbon impurities in the substrate and obviously improve the single-layer rate of graphene.
The technical scheme is as follows:
a preparation method of a graphene film growth substrate comprises the following steps:
(1) providing a copper foil substrate, wherein the copper foil substrate is provided with a first surface and a second surface opposite to the first surface;
(2) after a protective film is pasted on the first surface, oxidizing the second surface to prepare an intermediate I;
(3) and removing the protective film of the intermediate I to expose the first surface.
In one embodiment, the oxidizing treatment of the other surface of the copper foil substrate includes:
contacting an oxidizing reagent with the other surface of the copper foil substrate to perform redox reaction;
the oxidizing agent is selected from H2O2And H2SO4Mixture of (1), NaClO2And NaOH, or persulfate base solutions.
In one embodiment, the copper foil substrate is a polycrystalline copper foil or a single crystal copper foil, the thickness of the copper foil is 10 μm to 100 μm, and the mass ratio of the copper foil to the oxidizing agent is 1: (0.01-5);
the temperature of the oxidation-reduction reaction is 20-100 ℃, and the time is 1-20 min.
In one embodiment, the protective film is made of one or more of polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylate rubber, polyethylene and optical cement.
In one embodiment, before the step of attaching the protective film to the first surface, the method further comprises the steps of cleaning and drying the copper foil substrate.
In one embodiment, the cleaning of the copper foil substrate comprises:
and carrying out first organic solvent cleaning, second organic solvent cleaning, water cleaning and acid cleaning on the copper foil substrate.
In one embodiment, the organic solvents used in the first organic solvent cleaning and the second organic solvent cleaning are respectively and independently selected from one or more of ethanol, acetone and isopropanol;
the acid reagent adopted by the acid washing is one or more selected from phosphoric acid, acetic acid, hydrochloric acid and nitric acid.
In one embodiment, after the step of preparing the intermediate I, the step of washing and drying the intermediate I is further included.
In one embodiment, the cleaning of the intermediate I comprises:
and (3) carrying out water washing and organic solvent washing treatment on the intermediate I.
In one embodiment, the intermediate I is subjected to organic solvent cleaning by using one or more organic solvents selected from ethanol, acetone and isopropanol.
The invention also provides a graphene film growth substrate, which is prepared by the preparation method of the graphene film growth substrate.
The invention also provides a preparation method of the batch graphene film, which comprises the following steps:
preparing a graphene film growth substrate according to the preparation method of the graphene film growth substrate;
annealing the graphene film growth substrate;
and forming the graphene film on the first surface of the annealed graphene film growth substrate by a chemical vapor deposition method.
In one embodiment, the annealing process comprises:
and (3) preserving the temperature of the graphene film growth substrate for 10 min-6 h at 700-1100 ℃, and then cooling to below 60 ℃ at a cooling rate of 10-30 ℃/min.
The invention has the following beneficial effects:
the preparation method of the graphene film growth substrate mainly comprises the steps of providing a copper foil substrate, attaching a protective film to one surface of the copper foil substrate, oxidizing the other surface of the copper foil substrate, and removing the protective film.
The oxidation treatment can enable copper to be converted into copper oxide, the copper oxide can be continuously decomposed in the annealing process of preparing graphene subsequently, trace oxygen is provided, the oxygen can be continuously combined with carbon impurities on the surface or inside of the copper foil to form carbon monoxide or carbon dioxide, and the carbon impurities are discharged along with air flow, so that the influence of the carbon impurities on the growth of the graphene at the subsequent stage is avoided, the single-layer rate of the graphene can be greatly improved, the crystal boundary, the defects and the wrinkles of the graphene film are reduced, and the quality of the graphene is improved. Furthermore, the oxidation treatment is simple to operate, can be carried out in a large batch in a roll-to-roll mode, can obviously improve the production efficiency of the copper foil substrate of the substrate, can be used for preparing the copper foil substrate in a large batch, and is combined with a preparation method of a large-batch graphene film to improve the production efficiency of the graphene film. Furthermore, only one surface of the copper foil is subjected to oxidation treatment, and the other surface of the copper foil is not subjected to oxidation treatment, so that the surface appearance of the copper foil with the first surface (used for subsequent graphene growth) can be prevented from being damaged, and the adverse effects of increased roughness and increased impurities are avoided.
Drawings
Fig. 1 is a picture of graphene prepared in example 5 of the present invention;
fig. 2 is a picture of graphene prepared in comparative example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The words "preferably," "more preferably," and the like, in the present disclosure mean embodiments of the disclosure that may, in some instances, provide certain benefits. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The invention provides a preparation method of a graphene film growth substrate capable of obviously reducing the content of carbon impurities.
The technical scheme is as follows:
a preparation method of a graphene film growth substrate comprises the following steps:
(1) providing a copper foil substrate, wherein the copper foil substrate is provided with a first surface and a second surface opposite to the first surface;
(2) after a protective film is pasted on the first surface, oxidizing the second surface to prepare an intermediate I;
(3) and removing the protective film of the intermediate I to expose the first surface.
The oxidation treatment can enable copper to be converted into copper oxide, the copper oxide can be continuously decomposed in the subsequent graphene preparation annealing process to provide trace oxygen, the oxygen can be continuously combined with carbon impurities on the surface or inside of the copper foil to form carbon monoxide or carbon dioxide, and the carbon monoxide or carbon dioxide is discharged along with air flow, so that the influence of the carbon impurities on the growth of the graphene in the subsequent stage is avoided, the single-layer rate of the graphene can be greatly improved, the crystal boundary, the defects and the wrinkles of the graphene film are reduced, and the quality of the graphene is improved. Furthermore, the oxidation treatment is simple to operate, can be carried out in a large batch in a roll-to-roll mode, can obviously improve the production efficiency of the copper foil substrate of the substrate, can be used for preparing the copper foil substrate in a large batch, and is combined with a preparation method of a large-batch graphene film to improve the production efficiency of the graphene film.
The preparation method of the graphene thin film growth substrate according to the present invention is more specifically described as follows:
step (1) providing a copper foil substrate having a first surface and a second surface opposite the first surface:
in one embodiment, the copper foil substrate is a polycrystalline copper foil or a single crystal copper foil. Further, the copper foil has a thickness of 10 to 100 μm.
Preferably, the copper foil substrate is subjected to a cleaning and drying process before the step (2) is performed. Most impurities on the surface of the copper foil substrate can be removed through cleaning treatment, and the quality of the graphene film can be further improved in the subsequent process.
In one embodiment, the cleaning of the copper foil substrate comprises:
and carrying out first organic solvent cleaning, second organic solvent cleaning, water cleaning and acid cleaning on the copper foil substrate.
Further, the organic solvents adopted by the first organic solvent cleaning and the second organic solvent cleaning are respectively and independently selected from one or more of ethanol, acetone and isopropanol; and/or the acid reagent adopted by the acid washing is one or more selected from phosphoric acid, acetic acid, hydrochloric acid (preferably dilute hydrochloric acid) and nitric acid (preferably dilute nitric acid).
In one embodiment, the copper foil substrate is cleaned in the order of a first organic solvent cleaning, a water cleaning, an acid cleaning, a water cleaning, and a second organic solvent cleaning. Wherein, the acid cleaning treatment can achieve the purpose of micro-etching the surface of the copper foil substrate, and further remove impurities on the surface of the copper foil.
In one embodiment, the cleaning of the copper foil substrate comprises:
firstly, cleaning a copper foil substrate in an organic solvent for 1-10 min, wherein the organic solvent is selected from one or more of ethanol, acetone and isopropanol;
secondly, cleaning the copper foil substrate obtained in the step one in deionized water for 1-10 min;
thirdly, cleaning the copper foil substrate obtained in the second step in an acid solvent for 1-10 min, wherein the acid reagent is one or more selected from phosphoric acid, acetic acid and dilute hydrochloric acid) and dilute nitric acid;
and fourthly, sequentially washing the copper foil substrate obtained in the third step in deionized water and an organic solvent for 1-10 min, wherein the organic solvent is one or more selected from ethanol, acetone and isopropanol.
In one embodiment, the copper foil substrate after being cleaned is dried by nitrogen blow drying or blower blow drying.
Step (2) performing protective film pasting treatment on the first surface of the copper foil substrate, and then performing oxidation treatment on the second surface of the copper foil substrate to prepare an intermediate I:
according to researches, compared with the method for oxidizing both surfaces of the copper foil, the method for oxidizing the surface of the copper foil substrate has the advantages that one surface of the copper foil substrate is protected, and the other surface of the copper foil substrate is oxidized, so that the quality of graphene can be improved better. Specifically, with the two-sided oxidation, the surface morphology of the first-surface (for subsequent graphene growth) copper foil will be damaged, which may cause increased roughness and increased impurities.
In one embodiment, the material of the protective film is one or more of polypropylene (PP, preferably, stretchable polypropylene OPP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), Acrylate Rubber (AR), polyethylene (PE, preferably, low density polyethylene LDPE), and optical clear adhesive (OCR). The protective film has the advantages of acid and alkali corrosion resistance and easy processing.
In one embodiment, the oxidizing the second surface comprises:
contacting an oxidizing agent with the second surface to perform a redox reaction;
the oxidizing agent is selected from H2O2And H2SO4Mixture of (1), NaClO2And NaOH, or persulfate base solutions. This is beneficial to control the oxidation reaction degree, and the uniformity is easy to control. The persulfate may be selected from Na2S2O8And K2S2O8At least one of (1).
In one embodiment, the oxidizing agent is selected from H2O2And H2SO4According to the mass ratio (1-2): (2-3) mixed mixture, or NaClO2And NaOH according to the mass ratio (3-4): (1-8) mixing the above components.
In one embodiment, the oxidizing agent is contacted with the surface of the copper foil substrate by painting, spraying, or floating the copper foil substrate on the oxidizing agent. This is beneficial to control the oxidation reaction degree, and the uniformity is easy to control.
In one embodiment, the mass ratio of the copper foil to the oxidizing agent is 1: (0.01-5); the temperature of the oxidation-reduction reaction is 20-100 ℃, and the time is 1-20 min.
It is understood that the mass ratio of the copper foil to the oxidizing agent includes, but is not limited to: 1: 0.01, 1: 0.02, 1: 0.03, 1: 0.04, 1: 0.05, 1: 0.06, 1: 0.07, 1: 0.08, 1: 0.09, 1: 0.1, 1: 0.2, 1: 0.3, 1: 0.4, 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9, 1: 1. 1: 1.2, 1: 1.5, 1: 1.8, 1: 2. 1: 2.2, 1: 2.5, 1: 2.8, 1: 3. 1: 3.2, 1: 3.5, 1: 3.8, 1: 4. 1: 4.2, 1: 4.5, 1: 4.8 and 1: 5.
it is understood that the reaction temperature of the copper foil with the oxidizing agent includes, but is not limited to: 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C and 100 deg.C; preferably, the reaction temperature of the copper foil and the oxidizing reagent is 20 ℃ to 70 ℃.
It is understood that the reaction time of the copper foil with the oxidizing agent includes, but is not limited to: 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min and 20 min.
Preferably, before step (3), the intermediate I is washed and dried. Therefore, the impurity content can be further reduced, and the influence of impurities on the quality of the graphene can be reduced.
In one embodiment, the cleaning of the intermediate I comprises:
and (3) carrying out water washing and organic solvent washing treatment on the intermediate I. Preferably, the oxidized surface of the intermediate I, which is not protected by the protective film, is cleaned.
Further, the organic solvent used for the organic solvent cleaning is selected from one or more of ethanol, acetone and isopropanol.
In one embodiment, the cleaning process for the intermediate I comprises:
firstly, cleaning the oxidized surface which is not protected by the protective film in the intermediate I in deionized water for 1-10 min;
and washing the intermediate I obtained in the step I in an organic solvent for 1-10 min, wherein the organic solvent is selected from one or more of ethanol, acetone and isopropanol.
In one embodiment, the drying manner of the drying treatment of the washed intermediate I is nitrogen blow drying or blower blow drying.
Removing the protective film to expose the first surface, and preparing a graphene film growth substrate with an oxidized single surface:
the protective film is used for protecting one surface of the copper foil substrate from being oxidized, so that the surface appearance of the first surface (used for later growing graphene) of the copper foil can be protected later. And removing the protective film, so that the whole graphene film growth substrate can be uniformly involved in subsequent annealing treatment, and the removal of surface carbon impurities in the annealing process is facilitated.
In one embodiment of the preparation method of the graphene film growth substrate, after the step (3) of removing the protective film to expose the first surface and preparing the graphene film growth substrate with an oxidized single surface, the preparation method further includes a step of annealing the graphene film growth substrate.
In one embodiment, the annealing process comprises:
and (3) preserving the temperature of the graphene film growth substrate for 10 min-6 h at 700-1100 ℃, and then cooling to below 60 ℃ at a cooling rate of 10-30 ℃/min. The copper oxide is reduced and impurities are removed by a high temperature annealing process.
It is understood that the holding temperature of the annealing process includes, but is not limited to: 700 deg.C, 720 deg.C, 750 deg.C, 760 deg.C, 780 deg.C, 800 deg.C, 820 deg.C, 850 deg.C, 860 deg.C, 880 deg.C, 900 deg.C, 920 deg.C, 950 deg.C, 960 deg.C, 980 deg.C, 1000 deg.C, 1020 deg.C, 1050 deg.C, 1060 deg.C, 1080 deg.C and 1100 deg.C; incubation times include, but are not limited to: 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, 32min, 35min, 38min, 40min, 42min, 45min, 48min, 50min, 52min, 55min, 58min, 60min, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h and 6 h; the cooling rate includes, but is not limited to: 10 deg.C/min, 15 deg.C/min, 20 deg.C/min, 25 deg.C/min and 30 deg.C/min. The temperature after annealing includes but is not limited to: 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃.
In one embodiment, the annealing process comprises:
and contacting the graphene film growth substrate with argon and hydrogen, heating the argon flow of 200-600 sccm and 10-100 sccm to 700-1100 ℃, preserving the temperature for 10-6 h, and then cooling to below 60 ℃ at a cooling rate of 10-30 ℃/min.
The invention also provides a graphene film growth substrate, which is prepared by the preparation method of the graphene film growth substrate.
The invention also provides a preparation method of the batch graphene film, which comprises the following steps:
preparing a graphene film growth substrate according to the preparation method of the graphene film growth substrate;
annealing the graphene film growth substrate;
and forming the graphene film on the first surface of the annealed graphene film growth substrate by a chemical vapor deposition method. It is understood that the surface is the surface subjected to the protective film attaching treatment in the step (2) and the protective film removing treatment in the step (3).
In one embodiment, the annealing process comprises:
and (3) preserving the temperature of the graphene film growth substrate for 10 min-6 h at 700-1100 ℃, and then cooling to below 60 ℃ at a cooling rate of 10-30 ℃/min. The copper oxide is reduced and impurities are removed by a high temperature annealing process.
It is understood that the incubation temperature of the annealing process includes, but is not limited to: 700 deg.C, 720 deg.C, 750 deg.C, 760 deg.C, 780 deg.C, 800 deg.C, 820 deg.C, 850 deg.C, 860 deg.C, 880 deg.C, 900 deg.C, 920 deg.C, 950 deg.C, 960 deg.C, 980 deg.C, 1000 deg.C, 1020 deg.C, 1050 deg.C, 1060 deg.C, 1080 deg.C and 1100 deg.C; incubation times include, but are not limited to: 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, 32min, 35min, 38min, 40min, 42min, 45min, 48min, 50min, 52min, 55min, 58min, 60min, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h and 6 h; the cooling rate includes, but is not limited to: 10 deg.C/min, 15 deg.C/min, 20 deg.C/min, 25 deg.C/min and 30 deg.C/min. The temperature after annealing includes but is not limited to: 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃.
In one embodiment, the annealing process comprises:
and (2) putting the graphene film growth substrate into a chemical vapor deposition furnace for annealing, introducing argon and hydrogen, raising the temperature to 700-1100 ℃ at the argon flow rate of 200-600 sccm and 10-100 sccm, preserving the temperature for 10-6 h, and then reducing the temperature to below 60 ℃ at the cooling rate of 10-30 ℃/min.
It is understood that if the annealing process is already completed during the preparation of the graphene thin film growth substrate, the annealing step may be omitted during the preparation of the graphene.
The specific embodiment is as follows:
example 1
The embodiment provides a graphene film growth substrate and a preparation method thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 carrying out ultrasonic cleaning on a polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 ultrasonic cleaning the copper foil substrate in water and ethanol for 5 minutes respectively; and blown dry using nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil floats on the liquid surface of the oxidation reagent for 15min, and the second surface which is not pasted with the PVC film is contacted with the oxidation reagent, and the oxidation reagent is NaClO with the mass concentration of 80g/L2And a mixed solution with a mass concentration of 25g/L NaOH, wherein the temperature of the reagent is 70 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and removing the PVC electrostatic film on the first surface.
Step four, annealing the substrate, and performing xps test:
4.1 putting the copper foil into a CVD furnace for annealing, introducing argon and hydrogen, raising the temperature to 1050 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then lowering the temperature to 60 ℃ at the cooling rate of 20 ℃/min.
4.2 the copper foil was removed and characterized by xps, and the relative carbon content of the surface was found to be 37.41%.
Example 2
The embodiment provides a graphene film growth substrate and a preparation method thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 carrying out ultrasonic cleaning on a polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 ultrasonic cleaning the copper foil substrate in water and ethanol for 5 minutes respectively; and blown dry using nitrogen.
Step two, carrying out protection film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil floats on the liquid surface of the oxidation reagent for 15min, and the second surface which is not pasted with the PVC film is contacted with the oxidation reagent, and the oxidation reagent is NaClO with the mass concentration of 80g/L2And a mixed solution with the mass concentration of 55g/L NaOH, wherein the temperature of the reagent is 50 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and removing the PVC electrostatic film on the first surface.
Step four, annealing the substrate, and performing xps test:
4.1 putting the copper foil into a CVD furnace for annealing, introducing argon and hydrogen, raising the temperature to 1050 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then lowering the temperature to 60 ℃ at the cooling rate of 20 ℃/min.
4.2 the copper foil was removed and characterized by xps, and the relative carbon content of the surface was found to be 37.75%.
Example 3
The embodiment provides a graphene film growth substrate and a preparation method thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning the polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 ultrasonic cleaning the copper foil substrate in water and ethanol for 5 minutes respectively; and blown dry using nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching, cleaning and drying a PVC electrostatic film to the first surface of the copper foil;
2.2 the copper foil floats on the liquid surface of the oxidation reagent for 15min, and the second surface which is not pasted with the PVC film is contacted with the oxidation reagent, and the oxidation reagent is NaClO with the mass concentration of 90g/L2And a mixed solution with a mass concentration of 25g/L NaOH, wherein the temperature of the reagent is 60 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and removing the PVC electrostatic film on the first surface.
Step four, annealing the substrate, and performing xps test:
4.1 putting the copper foil into a CVD furnace for annealing, introducing argon and hydrogen, raising the temperature to 1050 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then lowering the temperature to 60 ℃ at the cooling rate of 20 ℃/min.
4.2 the copper foil was removed and characterized by xps, and the relative carbon content of the surface was found to be 37.88%.
Example 4
The embodiment provides a graphene film growth substrate and a preparation method thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning the polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 ultrasonic cleaning the copper foil substrate in water and ethanol for 5 minutes respectively; and blown dry using nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil floats on the liquid surface of the oxidation reagent for 15min, and the second surface which is not pasted with the PVC film is contacted with the oxidation reagent, and the oxidation reagent is NaClO with the mass concentration of 100g/L2And a mixed solution of NaOH with a mass concentration of 25g/L, wherein the temperature of the reagent is 70 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and removing the PVC electrostatic film on the first surface.
Step four, annealing the substrate, and performing xps test:
4.1 putting the copper foil into a CVD furnace for annealing, introducing argon and hydrogen, raising the temperature to 1050 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then lowering the temperature to 60 ℃ at the cooling rate of 20 ℃/min.
4.2 the copper foil was removed and xps characterization was performed and the relative carbon content on the surface was 37.48%.
Example 5
The embodiment provides a graphene film growth substrate and a preparation method and application thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning the polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 the copper foil substrate was ultrasonically cleaned in water, ethanol, then for 5 minutes each, and blown dry with nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil floats on the liquid surface of the oxidation reagent for 15min, and the second surface which is not pasted with the PVC film is contacted with the oxidation reagent, and the oxidation reagent is NaClO with the mass concentration of 80g/L2And a mixed solution with a mass concentration of 25g/L NaOH, wherein the temperature of the reagent is 70 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and then removing the PVC electrostatic film on the first surface.
Step four, carrying out graphene growth on the first surface of the substrate, and observing:
4.1 putting the copper foil into a CVD furnace, introducing argon and hydrogen into the CVD furnace, raising the temperature to 1030 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then introducing CH of 6sccm4For 10 minutes, after which CH is terminated4Introducing gas, and cooling to 60 ℃ at a cooling rate of 20 ℃/min.
4.2 the copper foil was removed and transferred to a silicon wafer, observed by an optical microscope, and the monolayer rate was calculated to be 96.8% using image pro software, since wrinkles and double-layer graphene are difficult to distinguish in the software, the actual monolayer rate should be higher, and the graphene picture is shown in fig. 1.
Example 6
The embodiment provides a graphene film growth substrate and a preparation method and application thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning the polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 the copper foil substrate was ultrasonically cleaned in water, ethanol, then for 5 minutes each, and blown dry with nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil is floated on the surface of the oxidizing reagent for 15min, and the second surface is contacted with the oxidizing reagent, wherein the oxidizing reagent is NaClO with the mass concentration of 80g/L2And a mixed solution with the mass concentration of 55g/L NaOH, wherein the temperature of the reagent is 50 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and then removing the PVC electrostatic film on the first surface.
Step four, carrying out graphene growth on the first surface of the substrate, and observing:
4.1 putting the copper foil into a CVD furnace, introducing argon and hydrogen into the CVD furnace, raising the temperature to 1030 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then introducing CH of 6sccm4For 10 minutes, after which CH is terminated4Introducing gas, and cooling to 60 ℃ at a cooling rate of 20 ℃/min.
4.2 the copper foil was taken out and transferred onto a silicon wafer, observed by an optical microscope, and the single layer rate was calculated to be 96.6% by using image pro software.
Example 7
The embodiment provides a graphene film growth substrate and a preparation method and application thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning the polycrystalline copper foil with the thickness of 25 mu m in an acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 the copper foil substrate was ultrasonically cleaned in water, ethanol, then for 5 minutes each, and blown dry with nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil is floated on the surface of the oxidizing reagent for 15min, and the second surface is contacted with the oxidizing reagent, wherein the oxidizing reagent is NaClO with the mass concentration of 90g/L2And a mixed solution with a mass concentration of 25g/L NaOH, wherein the temperature of the reagent is 60 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and then removing the PVC electrostatic film on the first surface.
Step four, carrying out graphene growth on the first surface of the substrate, and observing:
4.1 putting the copper foil into a CVD furnace, introducing argon and hydrogen into the CVD furnace, raising the temperature to 1030 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then introducing CH of 6sccm4For 10 minutes, after which CH is terminated4Introducing gas, and cooling to 60 ℃ at a cooling rate of 20 ℃/min.
4.2 the copper foil was taken out and transferred onto a silicon wafer, observed by an optical microscope, and the single layer rate was calculated to be 95.6% using software by image pro.
Example 8
The embodiment provides a graphene film growth substrate and a preparation method and application thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning of 25 μm thick copper foil in acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 the copper foil substrate was ultrasonically cleaned in water, ethanol, then for 5 minutes each, and blown dry with nitrogen.
Step two, carrying out protective film pasting treatment on the first surface of the substrate, and carrying out oxidation treatment on the second surface:
2.1 attaching a PVC electrostatic film to the first surface of the cleaned and dried copper foil;
2.2 the copper foil is floated on the surface of the oxidizing reagent for 15min, and the second surface is contacted with the oxidizing reagent, wherein the oxidizing reagent is NaClO with the mass concentration of 100g/L2And a mixed solution with a mass concentration of 25g/L NaOH, wherein the temperature of the reagent is 70 ℃, and the mass ratio of the copper foil to the oxidation reagent is 4: 1.
step three, cleaning and drying the second surface of the substrate:
3.1 ultrasonic cleaning the second surface of the copper foil after the oxidation treatment for 5 minutes in deionized water and ethanol respectively, then blowing nitrogen for drying, and then removing the PVC electrostatic film on the first surface.
Step four, carrying out graphene growth on the first surface of the substrate, and observing:
4.1 putting the copper foil into a CVD furnace, introducing argon and hydrogen into the CVD furnace, raising the temperature to 1030 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then introducing CH of 6sccm4For 10 minutes, after which CH is terminated4Introducing gas, and cooling to 60 ℃ at a cooling rate of 20 ℃/min.
4.2 the copper foil was taken out and transferred onto a silicon wafer, observed by an optical microscope, and the single layer rate was calculated to be 96.4% using image pro software.
Comparative example 1
The present comparative example provides a graphene thin film growth substrate and a method for preparing the same. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning of 25 μm thick copper foil in acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 the copper foil substrate was ultrasonically cleaned in water, ethanol, then for 5 minutes each, and blown dry with nitrogen.
Step two, annealing the substrate, and performing xps test:
2.1 putting the copper foil into a CVD furnace for annealing, introducing argon and hydrogen, raising the temperature to 1050 ℃ at the flow rates of 500sccm and 50sccm respectively, continuing for 30 minutes, and then reducing the temperature.
2.2 the copper foil was removed and subjected to xps characterization, resulting in a surface carbon content of 53.19%. Comparing example 1 with comparative example 1, it can be seen that the technical scheme of the application can reduce the carbon content on the surface of the copper foil.
Comparative example 2
The comparative example provides a graphene film growth substrate and a preparation method and application thereof. The method comprises the following specific steps:
step one, cleaning two surfaces of a substrate:
1.1 ultrasonic cleaning of 25 μm thick copper foil in acetone solution for 5 minutes;
1.2 ultrasonic cleaning the copper foil in water and acetic acid for 5 minutes respectively;
1.3 the copper foil substrate was ultrasonically cleaned in water, ethanol, then for 5 minutes each, and blown dry with nitrogen.
Step two, carrying out graphene growth on the surface of the substrate one, and observing:
2.1 placing the copper foil into a CVD furnace, introducing argon and hydrogen with the flow rates of 500sccm and 50sccm respectively, heating to 1030 ℃, keeping for 30 minutes, and then introducing 6sccm CH4For 10 minutes, after which CH is terminated4Introducing gas and cooling.
2.2 the copper foil was taken out and transferred onto a silicon wafer, observed by an optical microscope, and the monolayer rate was calculated to be 48.2% using image pro software, and the graphene picture is shown in FIG. 2. As can be seen from the comparison of example 5 and comparative example 2, the technical scheme of the application can significantly improve the single-layer rate of graphene grown on the surface of the copper foil.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims and drawings.
Claims (12)
1. A preparation method of a graphene film growth substrate is characterized by comprising the following steps:
(1) providing a copper foil substrate, wherein the copper foil substrate is provided with a first surface and a second surface opposite to the first surface;
(2) after a protective film is pasted on the first surface, carrying out oxidation treatment on the second surface to prepare an intermediate I;
(3) and removing the protective film to expose the first surface.
2. The method for preparing the graphene thin film growth substrate according to claim 1, wherein the step of oxidizing the second surface comprises:
contacting an oxidizing agent with the second surface to perform a redox reaction;
the oxidizing agent is selected from H2O2And H2SO4Mixture of (1), NaClO2And NaOH, or persulfate alkaline solutions.
3. The method for preparing the graphene film growth substrate according to claim 2, wherein the copper foil substrate is a polycrystalline copper foil or a single crystal copper foil, the thickness of the copper foil is 10 μm to 100 μm, and the mass ratio of the copper foil to the oxidizing agent is 1: (0.01-5);
the temperature of the oxidation-reduction reaction is 20-100 ℃, and the time is 1-20 min.
4. The method for preparing the graphene film growth substrate according to claim 1, wherein the protective film is made of one or more of polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylate rubber, polyethylene and optical cement.
5. The method for preparing the graphene film growth substrate according to any one of claims 1 to 4, wherein before the step of attaching the protective film to the first surface, the method further comprises the steps of cleaning and drying the copper foil substrate.
6. The method for preparing the graphene thin film growth substrate according to claim 5, wherein the cleaning of the copper foil substrate comprises:
and carrying out first organic solvent cleaning, second organic solvent cleaning, water cleaning and acid cleaning on the copper foil substrate.
7. The method for preparing the graphene thin film growth substrate according to claim 6, wherein the organic solvents used for the first organic solvent cleaning and the second organic solvent cleaning are respectively and independently selected from one or more of ethanol, acetone and isopropanol; and/or
The acid reagent adopted by the acid washing is one or more selected from phosphoric acid, acetic acid, hydrochloric acid and nitric acid.
8. The method for preparing the graphene thin film growth substrate according to any one of claims 1 to 4, wherein the method further comprises the steps of washing the intermediate I with water, washing with an organic solvent, and drying after the step of preparing the intermediate I.
9. The method for preparing the graphene thin film growth substrate according to claim 8, wherein the organic solvent used for cleaning the graphene thin film growth substrate is selected from one or more of ethanol, acetone and isopropanol.
10. A graphene thin film growth substrate, which is prepared by the method for preparing a graphene thin film growth substrate according to any one of claims 1 to 9.
11. A preparation method of a batch graphene film is characterized by comprising the following steps:
preparing a graphene thin film growth substrate according to the method for preparing a graphene thin film growth substrate of any one of claims 1 to 9;
annealing the graphene film growth substrate;
and forming the graphene film on the first surface of the annealed graphene film growth substrate by a chemical vapor deposition method.
12. The batch graphene film preparation method according to claim 11, wherein the annealing treatment comprises:
and (3) preserving the temperature of the graphene film growth substrate for 10 min-6 h at 700-1100 ℃, and then cooling to below 60 ℃ at a cooling rate of 10-30 ℃/min.
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